CA2440071A1 - Process to prepare a waxy raffinate - Google Patents
Process to prepare a waxy raffinate Download PDFInfo
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- CA2440071A1 CA2440071A1 CA002440071A CA2440071A CA2440071A1 CA 2440071 A1 CA2440071 A1 CA 2440071A1 CA 002440071 A CA002440071 A CA 002440071A CA 2440071 A CA2440071 A CA 2440071A CA 2440071 A1 CA2440071 A1 CA 2440071A1
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- waxy raffinate
- tropsch
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/02—Specified values of viscosity or viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/06—Gasoil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/08—Jet fuel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/17—Fisher Tropsch reaction products
- C10M2205/173—Fisher Tropsch reaction products used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S208/00—Mineral oils: processes and products
- Y10S208/95—Processing of "fischer-tropsch" crude
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- Engineering & Computer Science (AREA)
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- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Process to prepare a waxy raffinate product by (a) hydrocraking/hydroisomerisating a Fisher-Tropsch derived feed, wherein weigh t ratio of compounds having a least 60 or more carbon atoms and compounds havi ng at least 30 carbon atoms inthe Fischer-Tropsch product is at least 0.2 and wherein at least 30 wt% of compounds in the Fischer-Tropsch dervided feed ha ve at least 30 carbon atoms, (b) isolating from the product of step (a) a waxy raffinate product having a T10 wt% boiling point of between 200 and 450~C an d a T90 wt% boiling poing of between 400 and 650 ~C.
Description
PROCESS TO PREPARE A WAXY RAFFINATE
The invention is directed to a process to prepare a waxy raffinate from a Fischer-Tropsch product. The waxy raffinate product as obtained in this process may find application as a feedstock to prepare a lubricating base oil. Said preparation of the base oil and the preparation of the waxy raffinate product may take place at different locations. Suitably the waxy raffinate product is prepared at the location where the Fischer-Tropsch product is prepared and the lubricating base oil is prepared at a location near the main markets for these products. Generally these locations will be different resulting in that the waxy raffinate products will have to be transported, for example by ship, to the lubricant base oil manufacturing location. This manner of preparing base oils is advantageous because only one product has to be shipped to the potential base oil and lubricant markets instead of transporting the various base oils grades which may be prepared from the waxy raffinate product. Applicants have now found a process to prepare such a waxy raffinate product, which is transportable and from which a novel class of base oils can be prepared.
Prior art base oils as described in for example WO-A-0014179, WO-A-0014183, WO-A-0014187 and WO-A-0014188 comprise at least 95 wt% of non-cyclic isoparaffins. WO-A-0118156 describes a base oil derived from a Fischer-Tropsch product having a naphthenics content of less than 100. Also the base oils as disclosed in applicant's patent applications EP-A-776959 or EP-A-668342 have been found to comprise less than 10 wt% of cyclo-paraffins.
Applicants repeated Example 2 and 3 of EP-A-776959 and base oils were obtained, from a waxy Fischer-Tropsch synthesis product, wherein the base oils consisted of respectively about 96 wto and 93 wto of iso- and normal paraffins. Applicants further prepared a base oil having a pour point of -21 °C by catalytic dewaxing a Shell MDS
Waxy Raffinate (as obtainable from Shell MDS Malaysia Sdn Bhd) using a catalyst comprising synthetic ferrierite and platinum according to the teaching of EP-A-668342 and found that the content of iso- and normal paraffins was about 94 wto. Thus these prior art base oils derived from a Fischer-Tropsch synthesis product had at least a cyclo-paraffin content of below 10 wt%. Furthermore the base oils as disclosed by the examples of application VJO-A-9920720 will not comprise a high cyclo-paraffin content. This because feedstock and preparation used in said examples is very similar to the feedstock and preparation to prepare the above prior ar.t samples based on EP-A-776959 and EP-A-668342.
Applicants have now found a method to prepare a waxy raffinate product, from which lubricating base oil composition can be prepared having a higher cyclo paraffin content and a resulting improved solvency when compared to the disclosed base oils. This is found to be advantageous in for example industrial formulations such as turbine oils and hydraulic oils comprising for the greater part the base oil according to the invention.
Furthermore the base oil compositions will cause seals in for example motor engines to swell more than the prior art base oils. This is advantageous because due to said swelling less lubricant loss will be observed in certain applications. Applicants have found that such a base oil is an excellent API Group III base oil having improved solvency properties.
The invention is directed to the following process.
Process to prepare a waxy raffinate product by 3 _ (a) hydrocracking/hydroisomerisating a Fischer-Tropsch derived feed, wherein weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms in the Fischer-Tropsch product is at least 0.2 and wherein at least 30 wto of compounds in the Fischer-Tropsch derived feed have at least 30 carbon atoms, (b) isolating from the product of step (a) a waxy raffinate product having a T10 wt% boiling point of between 200 and 450 °C and a T90 wto boiling point of between 400 and 650 °C.
Applicants found that by performing the hydro-cracking/hydroisomerisation step with the relatively heavy feedstock a way raffinate product is obtained from which valuable products may be prepared, such as the base oil product as described in this application. A further advantage is that both fuels, for example gas oil, and a waxy raffinate product suited for preparing base oils are prepared in one hydrocracking/hydroisomerisation process step.
The process of the present invention also results in middle distillates having exceptionally good cold flow properties. These excellent cold flow properties could perhaps be explained by the relatively high ratio iso/normal and especially the relatively high amount of di- and/or trimethyl compounds. Nevertheless, the cetane number of the diesel fraction is more than excellent at values far exceeding 60, often values of 70 or more are obtained. In addition, the sulphur content is extremely low, always less than 50 ppmw, usually less than 5 ppmw and in most case the sulphur content is zero. Further, the density of especially the diesel fraction is less than 800 kg/m3, in most cases a density is observed between 765 and 790 kg/m3, usually around 780 kg/m3 (the viscosity at 100 °C for such a sample being about 3.0 cSt). Aromatic compounds are virtually absent, i.e.
less than 50 ppmw, resulting in very low particulate emissions. The po.lyaromatic content is even much lower than the aromatic content, usually less than 1 ppmw. T95, in combination with the above properties, is below 380 °C, often below 350 °C.
The process as described above results in middle distillates having extremely good cold flow properties.
For instance, the cloud point of any diesel fraction is usually below -18 °C, often even lower than -24 °C. The CFPP is usually below -20 °C, often -28 °C or lower. The pour point is usually below -18 °C, often below -24 °C.
The relatively heavy Fischer-Tropsch derived feed as used in step (a) has at least 30 wto, preferably at least 50 wto, and more preferably at least 55 wto of compounds having at least 30 carbon atoms. Furthermore the weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms of the Fischer-Tropsch derived feed is at least 0.2, preferably at least 0.4 and more preferably at least 0.55. The Fischer-Tropsch derived feed is preferably derived from a Fischer-Tropsch product which comprises a C20+ fraction having an ASF-alpha value (Anderson-Schulz-Flory chain growth factor) of at least 0.925, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955.
The initial boiling point of the Fischer-Tropsch derived feed may range up to 400 °C, but is preferably below 200 °C. Preferably at least any compounds having 4 or less carbon atoms and any compounds having a boiling point in that range are separated from a Fischer-Tropsch synthesis product before the Fischer-Tropsch synthesis product is used as a Fischer-Tropsch derived feed in step (a). The Fischer-Tropsch derived feed as described in detail above will for the greater part comprise of a Fischer-Tropsch synthesis product, which has not been subjected to a hydroconversion step as defined according to the present invention. The content of non-branched compounds in the Fischer-Tropsch synthesis product will therefore be above 80 wto. In addition to this Fischer-Tropsch product also other fractions may be part of the Fischer-Tropsch derived feed. Possible other fractions may suitably be any high boiling fraction obtained in step (b) or any surplus waxy raffinate product, which cannot be shipped away to lubricating manufactures. By recycling this fraction additional middle distillates may be prepared.
Such a Fischer-Tropsch derived feed is suitably obtained by a Fischer-Tropsch process, which yields a relatively heavy Fischer-Tropsch product. Not all Fischer-Tropsch processes yield such a heavy product. An example of a suitable Fischer-Tropsch process is described in WO-A-9934917 and in AU-A-698392. These processes may yield a Fischer-Tropsch product as described above.
The Fischer-Tropsch derived feed and the resulting waxy raffinate product will contain no or very little sulphur and nitrogen containing compounds. This is typical for a product derived from a Fischer-Tropsch reaction, which uses synthesis gas containing almost no impurities. Sulphur and nitrogen levels will generally be below the detection limits, which are currently 5 ppm for sulphur and 1 ppm for nitrogen.
The Fischer-Tropsch derived feed may optionally be subjected to a mild hydrotreatment step in order to remove any oxygenates and saturate any olefinic compounds present in the reaction product of the Fischer-Tropsch reaction. Such a hydrotreatment is described in EP-B-668342. The mildness of the hydrotreating step is preferably expressed in that the degree of conversion in this step is less than 20 wto and more preferably less than 10 wto. The conversion is here defined as the weight percentage of the feed boiling above 370 °C, which reacts to a fraction boiling below 370 °C. After such a mild hydrotreatment lower boiling compounds, having four or less carbon atoms and other compounds boiling in that range, will preferably be removed from the effluent before it is used in step (a).
The hydrocracking/hydroisomerisation reaction of step (a) is preferably performed in the presence of hydrogen and a catalyst, which catalyst can be chosen from those known to one skilled in the art as being suitable for this reaction. Catalysts for use in step (a) typically comprise an acidic functionality and a hydrogenation/dehydrogenation functionality. Preferred acidic functionality's are refractory metal oxide carriers. Suitable carrier materials include silica, alumina, silica-alumina, zirconia, titania and mixtures thereof. Preferred carrier materials for inclusion in the catalyst for use in the process of this invention are silica, alumina and silica-alumina. A particularly preferred catalyst comprises platinum supported on a silica-alumina carrier. If desired, applying a halogen moiety, in particular fluorine, or a phosphorous moiety to the carrier, may enhance the acidity of the catalyst carrier. Examples of suitable hydrocracking/hydro-isomerisation processes and suitable catalysts are described in WO-A-0014179, EP-A-532118, EP-A-666894 and the earlier referred to EP-A-776959.
Preferred hydrogenation/dehydrogenation functionalities are Group VIII non-noble metals, for example nickel and cobalt, optionally in combination with molybdenum or copper, and Group VIII noble metals, for _ 7 _ example palladium and more preferably platinum or platinum/palladium alloys. The catalyst may comprise the noble metal hydrogenation/dehydrogenation active component in an amount of from 0.005 to 5 parts by weight, preferably from 0.02 to 2 parts by weight, per 100 parts by weight of carrier material. A particularly preferred catalyst for use in the hydroconversion stage comprises platinum in an amount in the range of from 0.05 to 2 parts by weight, more preferably from 0.1 to 1 parts by weight, per 100 parts by weight of carrier material.
The catalyst may also comprise a binder to enhance the strength of the catalyst. The binder can be non-acidic.
Examples are clays and other binders known to one skilled in the art.
In step (a) the feed is contacted with hydrogen in the presence of the catalyst at elevated temperature and pressure. The temperatures typically will be in the range of from 175 to 380 °C, preferably higher than 250 °C and more preferably from 300 to 370 °C. The pressure will typically be in the range of from 10 to 250 bar and preferably between 20 and 80 bar. Hydrogen may be supplied at a gas hourly space velocity of from 100 to 10000 Nl/1/hr, preferably from 500 to 5000 N1/1/hr. The hydrocarbon feed may be provided at a weight hourly space velocity of from 0.1 to 5 kg/1/hr, preferably higher than 0.5 kg/1/hr and more preferably lower than 2 kg/1/hr. The ratio of hydrogen to hydrocarbon feed may range from 100 to 5000 N1/kg and is preferably from 250 to 2500 N1/kg.
The conversion in step (a) as defined as the weight percentage of the feed boiling above 370 °C which reacts per pass to a fraction boiling below 370 °C, is at least 20 wto, preferably at least 25 wto, but preferably not more than 80 wto, more preferably not more than 70 wto.
The feed as used above in the definition is the total hydrocarbon feed fed to step (a), thus also any optional _ g _ recycle of the higher boiling fraction as obtained in step (b) .
In step (b) the product of step (a) is separated into one or more gas oil fractions, a waxy raffinate product having a T10 wto boiling point of between 200 and 450 °C
and a T90 wto boiling point of between 400 and 650 °C and more preferably a T90wto boiling point of below 550 °C.
Depending on the conversion in step (a) and the properties of the total feed to step (a) also a higher boiling fraction may be obtained in step (b).
The separation in step (b) is preferably performed by means of a first distillation at about atmospheric' conditions, preferably at a pressure of between 1.2-2 bara, wherein the gas oil product and lower boiling fractions, such as naphtha and kerosine fractions, are separated from the higher boiling fraction of the product of step (a). The higher boiling fraction, of which suitably at least 95 wto boils above 370 °C, is subsequently further separated in a vacuum distillation step wherein a vacuum gas oil fraction, the waxy raffinate product and the higher boiling fraction are obtained. The vacuum distillation is suitably performed at a pressure of between 0.001. and 0.05 bara.
The vacuum distillation of step (b) is preferably operated such that the desired waxy raffinate product is obtained boiling in the specified range and having a kinematic viscosity at 100 °C of preferably between 3 and 10 cSt.
The waxy raffinate product as obtained by the above process has properties, such as pour point and viscosity, which makes it suitable to be transported, suitable by ships, to a lubricating base oil manufacturing location.
Preferably the waxy raffinate is stored and transported in the absence of oxygen such to avoid oxidation of the paraffin molecules present in the waxy raffinate product.
Suitable nitrogen blanketing is applied during said storage and transport. Preferably the waxy raffinate product has a pour point of above 0 °C. This makes it possible to transport the waxy raffinate as a solid by for example keeping the product at ambient temperatures.
Transporting the product in the solid state is advantageous because it further limits the ingress of oxygen and thus avoids oxidation. Means to liquefy the product at the unloading facility should be present.
Preferably indirect heating means such as steam heated coils are present in the storage tanks, such that the product may be liquefied before being discharged from the tanks. Transport lines are also preferably provided with means to keep the product in a liquid state.
The waxy raffinate product may find various applications. A most suited application is to use the waxy raffinate product as feedstock to prepare lubricating base oils by subjecting the waxy raffinate product to a pour point reducing step. Optionally the waxy raffinate product may be blended with slack wax in order to upgrade the slack wax properties with respect to sulphur,. nitrogen and saturates content before subjecting the waxy raffinate to a pour point reducing step.
With a pour point reducing treatment is understood every process wherein the pour point of the base oil is reduced by more than 10 °C, preferably more than 20 °C, more preferably more than 25 °C.
The pour point reducing treatment can be performed by means of a so-called solvent dewaxing process or by means of a catalytic dewaxing process. Solvent dewaxing is well known to those skilled in the art and involves admixture of one or more solvents and/or wax precipitating agents with the waxy raffinate product and cooling the mixture to a temperature in the range of from -10 °C to -40 °C, preferably in the range of from -20 °C to -35 °C, to separate the wax from the oil. The oil containing the wax is usually filtered through a filter cloth which can be made of textile fibres, such as cotton; porous metal cloth; or cloth made of synthetic materials. Examples of solvents which may be employed in the solvent dewaxing process are C3-C6 ketones (e. g. methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof), C6-C10 aromatic hydrocarbons (e. g. toluene), mixtures of ketones and aromatics (e. g. methyl ethyl ketone and toluene), autorefrigerative solvents such~as liquefied, normally gaseous C2-C4 hydrocarbons such as propane, propylene, butane, butylene and mixtures thereof. Mixtures of methyl ethyl ketone and toluene or methyl ethyl ketone and methyl isobutyl ketone are generally preferred. Examples of these and other suitable solvent dewaxing processes are described in Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr, Marcel Dekker Inc., New York, 1994, Chapter 7.
A preferred pour point reducing process is the catalytic dewaxing process. With such a process it has been found that base oils having a pour point of even below -40 °C can be prepared when starting from the waxy raffinate product according to the present process.
The catalytic dewaxing process can be performed by any process wherein in the presence of a catalyst and hydrogen the pour point of the waxy raffinate product is reduced as specified above. Suitable dewaxing catalysts are heterogeneous catalysts comprising a molecular sieve and optionally in combination with a metal having a hydrogenation function, such as the Group VIII metals.
Molecular sieves, and more.suitably intermediate pore size zeolites, have shown a good catalytic ability to reduce the pour point of the waxy raffinate product under catalytic dewaxing conditions. Preferably the .
intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 nm. Suitable intermediate pore size zeolites are mordenite, ZSM-5, ZSM-12, ZSM-22, ZSM-23, SSZ-32, ZSM-35 and ZSM-48. Another preferred group of molecular sieves are the silica-aluminaphosphate (SAPO) materials of which SAPO-11 is most preferred as for example described in US-A-4859311. ZSM-5 may optionally be used in its HZSM-5 form in the absence of any Group VIII metal. The other molecular sieves are preferably used in combination with an added Group VIII
metal. Suitable Group VIII metals are nickel, cobalt, platinum and palladium. Examples of possible combinations are Pt/ZSM-35, Ni/ZSM-5, Pt/ZSM-23, Pd/ZSM-23, Pt/ZSM-48 and Pt/SAPO-11. Further details and examples of suitable molecular sieves and dewaxing conditions are for example described in WO-A-9718278, US-A-4343692, US-A-5053373, US-A-5252527 and US-A-4574043.
The dewaxing catalyst suitably also comprises a binder. The binder can be a synthetic or naturally occurring (inorganic) substance, for example clay, silica and/or metal oxides. Natural occurring clays are for example of the montmorillonite and kaolin families. The binder is preferably a porous binder material, for example a refractory oxide of which examples are:
alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titanic as well as ternary compositions for example silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. More preferably a low acidity refractory oxide binder material, which is essentially free of alumina, is used. Examples of these binder materials are silica, zirconia, titanium dioxide, germanium dioxide, boric and mixtures of twoeor more of these of which examples are listed above. The most preferred binder is silica.
A preferred class of dewaxing catalysts comprise intermediate zeolite crystallites as described above and a low acidity refractory oxide binder material which is essentially free of alumina as described above, wherein the surface of the aluminosilicate zeolite crystallites has been modified by subjecting the aluminosilicate zeolite crystallites to a surface dealumination treatment. A preferred dealumination treatment is by contacting an extrudate of the binder and the zeolite with an aqueous solution of a fluorosilicate salt as described in for example US-A-5157191 or WO-A-0029511.
Examples of suitable dewaxing catalysts as described above are silica bound and dealuminated Pt/ZSM-5, and more preferably silica bound and dealuminated Pt/ZSM-23, silica bound and dealuminated Pt/ZSM-12, silica bound and dealuminated Pt/ZSM-22, as for example described in WO-A-0029511 and EP-B-832171.
Catalytic dewaxing conditions are known in the art and typically involve operating temperatures in the range of from 200 to 500 °C, suitably from 250 to 400 °C, hydrogen pressures in the range of from 10 to 200 bar, preferably from 40 to 70 bar, weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/1/hr), suitably from 0.2 to 5 kg/1/hr, more suitably from 0.5 to 3 kg/1/hr and hydrogen to oil ratios in the range of from 100 to 2,000 litres of hydrogen per litre of oil. By varying the temperature between 275, suitably between 315 and 375 °C at between 40-70 bars, in the catalytic dewaxing step it is possible to prepare base oils having different pour point specifications varying from suitably -10 to -60 °C.
The effluent or separate boiling fractions of the catalytic or solvent dewaxing step are optionally subjected to an additional hydrogenation step, also referred to as a hydrofinishing step for example if the effluent contains olefins or when the product is sensitive to oxygenation or when colour needs to be improved. This step is suitably carried out at a temperature between 180 and 380 °C, a total pressure of between 10 to 250 bar and preferably above 100 bar and more preferably between 120 and 250 bar. The WHSV (Weight hourly space velocity) ranges from 0.3 to 2 kg of oil per litre of catalyst per hour (kg/l.h).
The hydrogenation catalyst is suitably a supported catalyst comprising a dispersed Group VIII metal.
Possible Group VIII metals are cobalt, nickel, palladium and platinum. Cobalt and nickel containing catalysts may also comprise a Group VIB metal, suitably molybdenum and tungsten. Suitable carrier or support materials are low acidity amorphous refractory oxides. Examples of suitable amorphous refractory oxides include inorganic oxides, such as alumina, silica, titania, zirconia, boria, silica-alumina, fluorided alumina, fluorided silica-alumina and mixtures of two or more of these.
Examples of suitable hydrogenation catalysts are nickel-molybdenum containing catalyst such as KF-847 and KF-8010 (AKZO Nobel) M-8-24 and M-8-25 (BASF), and C-424, DN-190, HDS-3 and HDS-4 (Criterion); nickel-tungsten containing catalysts such as NI-4342 and NI-4352 (Engelhard) and C-454 (Criterion); cobalt-molybdenum containing catalysts such as KF-330 (AKZO-Nobel), HDS-22 (Criterion) and HPC-601 (Engelhard). Preferably platinum containing and more preferably platinum and palladium containing catalysts are used. Preferred supports for these palladium and/or platinum containing catalysts are amorphous silica-alumina. Examples of suitable silica-alumina carriers are disclosed in WO-A-9410263. A
preferred catalyst comprises an alloy of palladium and platinum preferably supported on an amorphous silica-alumina carrier of which the commercially available catalyst C-624 of Criterion Catalyst Company (Houston, TX) is, an example.
The dewaxed product is suitable separated into one or more base oil products having different viscosities by means of distillation, optionally in combination with an initial flashing step. The separation into the various fractions may suitably be performed in a vacuum distillation column provided with side stripers to separate the fraction from said column. In this mode it is found possible to obtain for example a base oil having a viscosity between 2-3 cSt, a base oil having a viscosity between 4-6 cSt and a base oil having a viscosity between 7-10 cSt product simultaneously from a single waxy raffinate product (viscosities as kinematic viscosity at 100 °C). By straightforward optimising the product slate and minimising the amount of non-base oil intermediate fractions it has been found possible to prepare base oils in a sufficiently high yield having a good Noack volatility properties. For example, base oils having a kinematic viscosity at 100 °C of between 3.5 and 6 cSt have been obtained which have a Noack volatility of between 6 and 14 wto.
It has been found that a lubricating base oil can be prepared starting from this waxy raffinate product which base oil comprises preferably at least 98 wt% saturates, more preferably at least 99.5 wto saturates and most preferably at least 99.9 wto. This saturates fraction in the base oil comprises between 10 and 40 wto of cyclo-paraffins. Preferably the content of cyclo-paraffins is less than 30 wto and more preferably less than 20 wto.
Preferably the content of cyclo-paraffins is at least 12 wto. The unique and novel base oils are~further characterized in that the weight ratio of 1-ring cyclo-paraffins relative to cyclo-paraffins having two or more rings is greater than 3 preferably greater than 5. It was found that this ratio is suitably smaller than 15.
The cyclo-paraffin content as described above is measured by the following method. Any other method resulting in the same results may also be used. The base oil sample is first separated into a polar (aromatic) phase and a non-polar (saturates) phase by making use of a high performance liquid chromatography (HPZC) method IP368/01, wherein as mobile phase pentane is used instead of hexane as the method states. The saturates and aromatic fractions are then analyzed using a Finnigan MAT90 mass spectrometer equipped with a Field desorption/Field Ionisation (FD/FI) interface, wherein FI
(a "soft" ionisation technique) is used for the semi-quantitative determination of hydrocarbon types in terms of carbon number and hydrogen deficiency. The type classification of compounds in mass spectrometry is determined by the characteristic ions formed and is normally classified by "z number". This is given by the general formula for all hydrocarbon species: CnH2n+z-Because the saturates phase is analysed separately from the aromatic phase it is possible to determine the content of the different (cyclo)-paraffins having the same stoichiometry. The results of the mass spectrometer are processed using commercial software (poly 32;
available from Sierra Analytics ZLC, 3453 Dragoo Park Drive, Modesto, California GA95350 USA) to determine the relative proportions of each hydrocarbon type and the average molecular weight and polydispersity of the saturates and aromatics fractions.
The base oil composition preferably has a content of aromatic hydrocarbon compounds of less than 1 wto, more preferably less than 0.5 wto and most preferably less than 0.1 wto, a sulphur content of less than 20 ppm and a nitrogen content of less than 20 ppm. The pour point of the base oil is preferably less than -30 °C and more preferably lower than -40 °C. The viscosity index is higher than 120. It has been found that the novel base oils typically have a viscosity index of below 140.
The base oils itself may find application as part of for example an Automatic Transmission Fluids (ATF), automotive (gasoline or diesel) engine oils, turbine oils, hydraulic oils, electrical oils or transformer oils and refrigerator oils.
The invention will be illustrated with the following non-limiting examples.
Example 1 A waxy raffinate product was obtained by feeding continuously a C5-C750 °C+ fraction of the Fischer-Tropsch product, as obtained in Example VII using the catalyst of Example III of WO-A-9934917 to a hydrocracking step (step (a)). The feed contained about 60 wto C30+ product. The ratio C60+/C30+ was about 0.55.
In the hydrocracking step the fraction was contacted with a hydrocracking catalyst. of Example 1 of EP-A-532118.
The effluent of step (a) was continuously distilled to give lights, fuels and a residue "R" boiling from 370 °C and above. The yield of gas oil fraction on fresh feed to hydrocracking step was 43 wto. The main part of the residue "R°' was recycled to step (a) and a remaining part was separated by means of a vacuum distillation into a waxy raffinate product having the properties as in Table 1 and a fraction boiling above 510 °C.
The conditions in the hydrocracking step (a) were: a fresh feed Weight Hourly Space Velocity (WHSV) of 0.8 kg/l.h, recycle feed WHSV of 0.2 kg/l.h, hydrogen gas rate = 1000 N1/kg, total pressure = 40 bar, and a reactor temperature of 335 °C.
Table 1 Density at 70C (kglm3) 779.2 vK@100 (cSt) 3.818 pour point (C) +18 Boiling point data as 5o 355 C
temperature at which a 100 370 C
wto is recovered.
Example 2 The waxy raffinate product of Example 1 was dewaxed to prepare a base oil by contacting the product with a dealuminated silica bound ZSM-5 catalyst comprising 0.70 by weight Pt and 30 wt% ZSM-5 as described in Example 9 of WO-A-0029511. The dewaxing conditions were 40 bar hydrogen, WHSV = 1 kg/l.h and a temperature of 340 °C.
The dewaxed oil was distilled into three base oil fractions: boiling between 378 and 424 °C (yield based on feed to dewaxing step was 14.2 wto), between 418-455 °C
(yield based on feed to dewaxing step was 16.3 wto) and a fraction boiling above 455 °C (yield based on feed to dewaxing step was 21.6 wto). See Table 2 for more details.
Table 2 Light Medium Heavy Grade Grade Gxade density at 20 C 805.8 814.6 822.4 pour point (C) < -63 < -51 - 45 kinematic viscosity at 19.06 35.0 40 C (cSt) kinematic viscosity at 100 C (cSt) 3.16 4.144 6.347 VI n.a. 121 134 Noack volatility (wto) n.a. 10.8 2.24 sulphur content (ppm) < 1 ppm < 1 ppm < 5 ppm saturates (ow) n.a. 99'.9 n.a.
Content of cyclo- n.a. 18.5 n.a.
paraffins (wt o ) ( *
) Dynamic viscosity as n.a. 3900 cP n.a.
measured by CCS at (*) as determined by means of a Finnigan MAT90 mass spectrometer equipped with a Field desorption/field ionisation interface on the saturates fraction of said base oil.
n.a.: not applicable n.d.: not determined Example 3 Example 2 was repeated except that the dewaxed oil was distilled into the different three base oil products of which the properties are presented in Table 3.
Table 3 Zight Medium Heavy Grade Grade Grade density at 20 C 809.1 817.2 825.1 pour point (C) < -63 < -51 - 39 kinematic viscosity at 23.32 43.01 40 C (cSt) kinematic viscosity at 100 C (cSt) 3.181 4.778 7.349 VI n.a. 128 135 Noack volatility (wto) n.a. 7.7 n.a.
sulphur content (ppm) < 5 ppm < 5 ppm < 5 ppm saturates (ow) 99.0 Dynamic viscosity as 5500 cP
measured by CCS at -40 C
Yield based on feed to 15.3 27.4 8.9 cat dewaxing step (wt%) Example 4 Example 2 was repeated except that the that the dewaxed oil was distilled into the different three base oil products and one intermediate raffinate (I.R.) of which the properties are presented in Table 4.
Table 4 Light I.R. Medium Heavy Grade Grade Grade density at 20 C 806 811.3 817.5 824.5 pour point (C) < -63 -57 < -51 - 39 Kinematic viscosity at 10.4 23.51 42.23 40 C (cSt) Kinematic viscosity at 100 C (cSt) 2.746 3.501 4.79 7.24 Noack volatility n.a. 6.8 1.14 sulphur content (ppm) < 5 ppm < 5 ppm < 5 ppm Saturates (ow) n.d. 99.5 Dynamic viscosity as 5500 cP
measured by CCS at Yield based on CDW feed 22.6 8.9 22.6 11.1 n.a.: not applicable n.d.: not determined Examples 2-4 illustrate that from the waxy raffinate product as obtained by the process of the present invention base oils are prepared in a high yield and wherein the base oils have excellent viscometric properties.
The invention is directed to a process to prepare a waxy raffinate from a Fischer-Tropsch product. The waxy raffinate product as obtained in this process may find application as a feedstock to prepare a lubricating base oil. Said preparation of the base oil and the preparation of the waxy raffinate product may take place at different locations. Suitably the waxy raffinate product is prepared at the location where the Fischer-Tropsch product is prepared and the lubricating base oil is prepared at a location near the main markets for these products. Generally these locations will be different resulting in that the waxy raffinate products will have to be transported, for example by ship, to the lubricant base oil manufacturing location. This manner of preparing base oils is advantageous because only one product has to be shipped to the potential base oil and lubricant markets instead of transporting the various base oils grades which may be prepared from the waxy raffinate product. Applicants have now found a process to prepare such a waxy raffinate product, which is transportable and from which a novel class of base oils can be prepared.
Prior art base oils as described in for example WO-A-0014179, WO-A-0014183, WO-A-0014187 and WO-A-0014188 comprise at least 95 wt% of non-cyclic isoparaffins. WO-A-0118156 describes a base oil derived from a Fischer-Tropsch product having a naphthenics content of less than 100. Also the base oils as disclosed in applicant's patent applications EP-A-776959 or EP-A-668342 have been found to comprise less than 10 wt% of cyclo-paraffins.
Applicants repeated Example 2 and 3 of EP-A-776959 and base oils were obtained, from a waxy Fischer-Tropsch synthesis product, wherein the base oils consisted of respectively about 96 wto and 93 wto of iso- and normal paraffins. Applicants further prepared a base oil having a pour point of -21 °C by catalytic dewaxing a Shell MDS
Waxy Raffinate (as obtainable from Shell MDS Malaysia Sdn Bhd) using a catalyst comprising synthetic ferrierite and platinum according to the teaching of EP-A-668342 and found that the content of iso- and normal paraffins was about 94 wto. Thus these prior art base oils derived from a Fischer-Tropsch synthesis product had at least a cyclo-paraffin content of below 10 wt%. Furthermore the base oils as disclosed by the examples of application VJO-A-9920720 will not comprise a high cyclo-paraffin content. This because feedstock and preparation used in said examples is very similar to the feedstock and preparation to prepare the above prior ar.t samples based on EP-A-776959 and EP-A-668342.
Applicants have now found a method to prepare a waxy raffinate product, from which lubricating base oil composition can be prepared having a higher cyclo paraffin content and a resulting improved solvency when compared to the disclosed base oils. This is found to be advantageous in for example industrial formulations such as turbine oils and hydraulic oils comprising for the greater part the base oil according to the invention.
Furthermore the base oil compositions will cause seals in for example motor engines to swell more than the prior art base oils. This is advantageous because due to said swelling less lubricant loss will be observed in certain applications. Applicants have found that such a base oil is an excellent API Group III base oil having improved solvency properties.
The invention is directed to the following process.
Process to prepare a waxy raffinate product by 3 _ (a) hydrocracking/hydroisomerisating a Fischer-Tropsch derived feed, wherein weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms in the Fischer-Tropsch product is at least 0.2 and wherein at least 30 wto of compounds in the Fischer-Tropsch derived feed have at least 30 carbon atoms, (b) isolating from the product of step (a) a waxy raffinate product having a T10 wt% boiling point of between 200 and 450 °C and a T90 wto boiling point of between 400 and 650 °C.
Applicants found that by performing the hydro-cracking/hydroisomerisation step with the relatively heavy feedstock a way raffinate product is obtained from which valuable products may be prepared, such as the base oil product as described in this application. A further advantage is that both fuels, for example gas oil, and a waxy raffinate product suited for preparing base oils are prepared in one hydrocracking/hydroisomerisation process step.
The process of the present invention also results in middle distillates having exceptionally good cold flow properties. These excellent cold flow properties could perhaps be explained by the relatively high ratio iso/normal and especially the relatively high amount of di- and/or trimethyl compounds. Nevertheless, the cetane number of the diesel fraction is more than excellent at values far exceeding 60, often values of 70 or more are obtained. In addition, the sulphur content is extremely low, always less than 50 ppmw, usually less than 5 ppmw and in most case the sulphur content is zero. Further, the density of especially the diesel fraction is less than 800 kg/m3, in most cases a density is observed between 765 and 790 kg/m3, usually around 780 kg/m3 (the viscosity at 100 °C for such a sample being about 3.0 cSt). Aromatic compounds are virtually absent, i.e.
less than 50 ppmw, resulting in very low particulate emissions. The po.lyaromatic content is even much lower than the aromatic content, usually less than 1 ppmw. T95, in combination with the above properties, is below 380 °C, often below 350 °C.
The process as described above results in middle distillates having extremely good cold flow properties.
For instance, the cloud point of any diesel fraction is usually below -18 °C, often even lower than -24 °C. The CFPP is usually below -20 °C, often -28 °C or lower. The pour point is usually below -18 °C, often below -24 °C.
The relatively heavy Fischer-Tropsch derived feed as used in step (a) has at least 30 wto, preferably at least 50 wto, and more preferably at least 55 wto of compounds having at least 30 carbon atoms. Furthermore the weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms of the Fischer-Tropsch derived feed is at least 0.2, preferably at least 0.4 and more preferably at least 0.55. The Fischer-Tropsch derived feed is preferably derived from a Fischer-Tropsch product which comprises a C20+ fraction having an ASF-alpha value (Anderson-Schulz-Flory chain growth factor) of at least 0.925, preferably at least 0.935, more preferably at least 0.945, even more preferably at least 0.955.
The initial boiling point of the Fischer-Tropsch derived feed may range up to 400 °C, but is preferably below 200 °C. Preferably at least any compounds having 4 or less carbon atoms and any compounds having a boiling point in that range are separated from a Fischer-Tropsch synthesis product before the Fischer-Tropsch synthesis product is used as a Fischer-Tropsch derived feed in step (a). The Fischer-Tropsch derived feed as described in detail above will for the greater part comprise of a Fischer-Tropsch synthesis product, which has not been subjected to a hydroconversion step as defined according to the present invention. The content of non-branched compounds in the Fischer-Tropsch synthesis product will therefore be above 80 wto. In addition to this Fischer-Tropsch product also other fractions may be part of the Fischer-Tropsch derived feed. Possible other fractions may suitably be any high boiling fraction obtained in step (b) or any surplus waxy raffinate product, which cannot be shipped away to lubricating manufactures. By recycling this fraction additional middle distillates may be prepared.
Such a Fischer-Tropsch derived feed is suitably obtained by a Fischer-Tropsch process, which yields a relatively heavy Fischer-Tropsch product. Not all Fischer-Tropsch processes yield such a heavy product. An example of a suitable Fischer-Tropsch process is described in WO-A-9934917 and in AU-A-698392. These processes may yield a Fischer-Tropsch product as described above.
The Fischer-Tropsch derived feed and the resulting waxy raffinate product will contain no or very little sulphur and nitrogen containing compounds. This is typical for a product derived from a Fischer-Tropsch reaction, which uses synthesis gas containing almost no impurities. Sulphur and nitrogen levels will generally be below the detection limits, which are currently 5 ppm for sulphur and 1 ppm for nitrogen.
The Fischer-Tropsch derived feed may optionally be subjected to a mild hydrotreatment step in order to remove any oxygenates and saturate any olefinic compounds present in the reaction product of the Fischer-Tropsch reaction. Such a hydrotreatment is described in EP-B-668342. The mildness of the hydrotreating step is preferably expressed in that the degree of conversion in this step is less than 20 wto and more preferably less than 10 wto. The conversion is here defined as the weight percentage of the feed boiling above 370 °C, which reacts to a fraction boiling below 370 °C. After such a mild hydrotreatment lower boiling compounds, having four or less carbon atoms and other compounds boiling in that range, will preferably be removed from the effluent before it is used in step (a).
The hydrocracking/hydroisomerisation reaction of step (a) is preferably performed in the presence of hydrogen and a catalyst, which catalyst can be chosen from those known to one skilled in the art as being suitable for this reaction. Catalysts for use in step (a) typically comprise an acidic functionality and a hydrogenation/dehydrogenation functionality. Preferred acidic functionality's are refractory metal oxide carriers. Suitable carrier materials include silica, alumina, silica-alumina, zirconia, titania and mixtures thereof. Preferred carrier materials for inclusion in the catalyst for use in the process of this invention are silica, alumina and silica-alumina. A particularly preferred catalyst comprises platinum supported on a silica-alumina carrier. If desired, applying a halogen moiety, in particular fluorine, or a phosphorous moiety to the carrier, may enhance the acidity of the catalyst carrier. Examples of suitable hydrocracking/hydro-isomerisation processes and suitable catalysts are described in WO-A-0014179, EP-A-532118, EP-A-666894 and the earlier referred to EP-A-776959.
Preferred hydrogenation/dehydrogenation functionalities are Group VIII non-noble metals, for example nickel and cobalt, optionally in combination with molybdenum or copper, and Group VIII noble metals, for _ 7 _ example palladium and more preferably platinum or platinum/palladium alloys. The catalyst may comprise the noble metal hydrogenation/dehydrogenation active component in an amount of from 0.005 to 5 parts by weight, preferably from 0.02 to 2 parts by weight, per 100 parts by weight of carrier material. A particularly preferred catalyst for use in the hydroconversion stage comprises platinum in an amount in the range of from 0.05 to 2 parts by weight, more preferably from 0.1 to 1 parts by weight, per 100 parts by weight of carrier material.
The catalyst may also comprise a binder to enhance the strength of the catalyst. The binder can be non-acidic.
Examples are clays and other binders known to one skilled in the art.
In step (a) the feed is contacted with hydrogen in the presence of the catalyst at elevated temperature and pressure. The temperatures typically will be in the range of from 175 to 380 °C, preferably higher than 250 °C and more preferably from 300 to 370 °C. The pressure will typically be in the range of from 10 to 250 bar and preferably between 20 and 80 bar. Hydrogen may be supplied at a gas hourly space velocity of from 100 to 10000 Nl/1/hr, preferably from 500 to 5000 N1/1/hr. The hydrocarbon feed may be provided at a weight hourly space velocity of from 0.1 to 5 kg/1/hr, preferably higher than 0.5 kg/1/hr and more preferably lower than 2 kg/1/hr. The ratio of hydrogen to hydrocarbon feed may range from 100 to 5000 N1/kg and is preferably from 250 to 2500 N1/kg.
The conversion in step (a) as defined as the weight percentage of the feed boiling above 370 °C which reacts per pass to a fraction boiling below 370 °C, is at least 20 wto, preferably at least 25 wto, but preferably not more than 80 wto, more preferably not more than 70 wto.
The feed as used above in the definition is the total hydrocarbon feed fed to step (a), thus also any optional _ g _ recycle of the higher boiling fraction as obtained in step (b) .
In step (b) the product of step (a) is separated into one or more gas oil fractions, a waxy raffinate product having a T10 wto boiling point of between 200 and 450 °C
and a T90 wto boiling point of between 400 and 650 °C and more preferably a T90wto boiling point of below 550 °C.
Depending on the conversion in step (a) and the properties of the total feed to step (a) also a higher boiling fraction may be obtained in step (b).
The separation in step (b) is preferably performed by means of a first distillation at about atmospheric' conditions, preferably at a pressure of between 1.2-2 bara, wherein the gas oil product and lower boiling fractions, such as naphtha and kerosine fractions, are separated from the higher boiling fraction of the product of step (a). The higher boiling fraction, of which suitably at least 95 wto boils above 370 °C, is subsequently further separated in a vacuum distillation step wherein a vacuum gas oil fraction, the waxy raffinate product and the higher boiling fraction are obtained. The vacuum distillation is suitably performed at a pressure of between 0.001. and 0.05 bara.
The vacuum distillation of step (b) is preferably operated such that the desired waxy raffinate product is obtained boiling in the specified range and having a kinematic viscosity at 100 °C of preferably between 3 and 10 cSt.
The waxy raffinate product as obtained by the above process has properties, such as pour point and viscosity, which makes it suitable to be transported, suitable by ships, to a lubricating base oil manufacturing location.
Preferably the waxy raffinate is stored and transported in the absence of oxygen such to avoid oxidation of the paraffin molecules present in the waxy raffinate product.
Suitable nitrogen blanketing is applied during said storage and transport. Preferably the waxy raffinate product has a pour point of above 0 °C. This makes it possible to transport the waxy raffinate as a solid by for example keeping the product at ambient temperatures.
Transporting the product in the solid state is advantageous because it further limits the ingress of oxygen and thus avoids oxidation. Means to liquefy the product at the unloading facility should be present.
Preferably indirect heating means such as steam heated coils are present in the storage tanks, such that the product may be liquefied before being discharged from the tanks. Transport lines are also preferably provided with means to keep the product in a liquid state.
The waxy raffinate product may find various applications. A most suited application is to use the waxy raffinate product as feedstock to prepare lubricating base oils by subjecting the waxy raffinate product to a pour point reducing step. Optionally the waxy raffinate product may be blended with slack wax in order to upgrade the slack wax properties with respect to sulphur,. nitrogen and saturates content before subjecting the waxy raffinate to a pour point reducing step.
With a pour point reducing treatment is understood every process wherein the pour point of the base oil is reduced by more than 10 °C, preferably more than 20 °C, more preferably more than 25 °C.
The pour point reducing treatment can be performed by means of a so-called solvent dewaxing process or by means of a catalytic dewaxing process. Solvent dewaxing is well known to those skilled in the art and involves admixture of one or more solvents and/or wax precipitating agents with the waxy raffinate product and cooling the mixture to a temperature in the range of from -10 °C to -40 °C, preferably in the range of from -20 °C to -35 °C, to separate the wax from the oil. The oil containing the wax is usually filtered through a filter cloth which can be made of textile fibres, such as cotton; porous metal cloth; or cloth made of synthetic materials. Examples of solvents which may be employed in the solvent dewaxing process are C3-C6 ketones (e. g. methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof), C6-C10 aromatic hydrocarbons (e. g. toluene), mixtures of ketones and aromatics (e. g. methyl ethyl ketone and toluene), autorefrigerative solvents such~as liquefied, normally gaseous C2-C4 hydrocarbons such as propane, propylene, butane, butylene and mixtures thereof. Mixtures of methyl ethyl ketone and toluene or methyl ethyl ketone and methyl isobutyl ketone are generally preferred. Examples of these and other suitable solvent dewaxing processes are described in Lubricant Base Oil and Wax Processing, Avilino Sequeira, Jr, Marcel Dekker Inc., New York, 1994, Chapter 7.
A preferred pour point reducing process is the catalytic dewaxing process. With such a process it has been found that base oils having a pour point of even below -40 °C can be prepared when starting from the waxy raffinate product according to the present process.
The catalytic dewaxing process can be performed by any process wherein in the presence of a catalyst and hydrogen the pour point of the waxy raffinate product is reduced as specified above. Suitable dewaxing catalysts are heterogeneous catalysts comprising a molecular sieve and optionally in combination with a metal having a hydrogenation function, such as the Group VIII metals.
Molecular sieves, and more.suitably intermediate pore size zeolites, have shown a good catalytic ability to reduce the pour point of the waxy raffinate product under catalytic dewaxing conditions. Preferably the .
intermediate pore size zeolites have a pore diameter of between 0.35 and 0.8 nm. Suitable intermediate pore size zeolites are mordenite, ZSM-5, ZSM-12, ZSM-22, ZSM-23, SSZ-32, ZSM-35 and ZSM-48. Another preferred group of molecular sieves are the silica-aluminaphosphate (SAPO) materials of which SAPO-11 is most preferred as for example described in US-A-4859311. ZSM-5 may optionally be used in its HZSM-5 form in the absence of any Group VIII metal. The other molecular sieves are preferably used in combination with an added Group VIII
metal. Suitable Group VIII metals are nickel, cobalt, platinum and palladium. Examples of possible combinations are Pt/ZSM-35, Ni/ZSM-5, Pt/ZSM-23, Pd/ZSM-23, Pt/ZSM-48 and Pt/SAPO-11. Further details and examples of suitable molecular sieves and dewaxing conditions are for example described in WO-A-9718278, US-A-4343692, US-A-5053373, US-A-5252527 and US-A-4574043.
The dewaxing catalyst suitably also comprises a binder. The binder can be a synthetic or naturally occurring (inorganic) substance, for example clay, silica and/or metal oxides. Natural occurring clays are for example of the montmorillonite and kaolin families. The binder is preferably a porous binder material, for example a refractory oxide of which examples are:
alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titanic as well as ternary compositions for example silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. More preferably a low acidity refractory oxide binder material, which is essentially free of alumina, is used. Examples of these binder materials are silica, zirconia, titanium dioxide, germanium dioxide, boric and mixtures of twoeor more of these of which examples are listed above. The most preferred binder is silica.
A preferred class of dewaxing catalysts comprise intermediate zeolite crystallites as described above and a low acidity refractory oxide binder material which is essentially free of alumina as described above, wherein the surface of the aluminosilicate zeolite crystallites has been modified by subjecting the aluminosilicate zeolite crystallites to a surface dealumination treatment. A preferred dealumination treatment is by contacting an extrudate of the binder and the zeolite with an aqueous solution of a fluorosilicate salt as described in for example US-A-5157191 or WO-A-0029511.
Examples of suitable dewaxing catalysts as described above are silica bound and dealuminated Pt/ZSM-5, and more preferably silica bound and dealuminated Pt/ZSM-23, silica bound and dealuminated Pt/ZSM-12, silica bound and dealuminated Pt/ZSM-22, as for example described in WO-A-0029511 and EP-B-832171.
Catalytic dewaxing conditions are known in the art and typically involve operating temperatures in the range of from 200 to 500 °C, suitably from 250 to 400 °C, hydrogen pressures in the range of from 10 to 200 bar, preferably from 40 to 70 bar, weight hourly space velocities (WHSV) in the range of from 0.1 to 10 kg of oil per litre of catalyst per hour (kg/1/hr), suitably from 0.2 to 5 kg/1/hr, more suitably from 0.5 to 3 kg/1/hr and hydrogen to oil ratios in the range of from 100 to 2,000 litres of hydrogen per litre of oil. By varying the temperature between 275, suitably between 315 and 375 °C at between 40-70 bars, in the catalytic dewaxing step it is possible to prepare base oils having different pour point specifications varying from suitably -10 to -60 °C.
The effluent or separate boiling fractions of the catalytic or solvent dewaxing step are optionally subjected to an additional hydrogenation step, also referred to as a hydrofinishing step for example if the effluent contains olefins or when the product is sensitive to oxygenation or when colour needs to be improved. This step is suitably carried out at a temperature between 180 and 380 °C, a total pressure of between 10 to 250 bar and preferably above 100 bar and more preferably between 120 and 250 bar. The WHSV (Weight hourly space velocity) ranges from 0.3 to 2 kg of oil per litre of catalyst per hour (kg/l.h).
The hydrogenation catalyst is suitably a supported catalyst comprising a dispersed Group VIII metal.
Possible Group VIII metals are cobalt, nickel, palladium and platinum. Cobalt and nickel containing catalysts may also comprise a Group VIB metal, suitably molybdenum and tungsten. Suitable carrier or support materials are low acidity amorphous refractory oxides. Examples of suitable amorphous refractory oxides include inorganic oxides, such as alumina, silica, titania, zirconia, boria, silica-alumina, fluorided alumina, fluorided silica-alumina and mixtures of two or more of these.
Examples of suitable hydrogenation catalysts are nickel-molybdenum containing catalyst such as KF-847 and KF-8010 (AKZO Nobel) M-8-24 and M-8-25 (BASF), and C-424, DN-190, HDS-3 and HDS-4 (Criterion); nickel-tungsten containing catalysts such as NI-4342 and NI-4352 (Engelhard) and C-454 (Criterion); cobalt-molybdenum containing catalysts such as KF-330 (AKZO-Nobel), HDS-22 (Criterion) and HPC-601 (Engelhard). Preferably platinum containing and more preferably platinum and palladium containing catalysts are used. Preferred supports for these palladium and/or platinum containing catalysts are amorphous silica-alumina. Examples of suitable silica-alumina carriers are disclosed in WO-A-9410263. A
preferred catalyst comprises an alloy of palladium and platinum preferably supported on an amorphous silica-alumina carrier of which the commercially available catalyst C-624 of Criterion Catalyst Company (Houston, TX) is, an example.
The dewaxed product is suitable separated into one or more base oil products having different viscosities by means of distillation, optionally in combination with an initial flashing step. The separation into the various fractions may suitably be performed in a vacuum distillation column provided with side stripers to separate the fraction from said column. In this mode it is found possible to obtain for example a base oil having a viscosity between 2-3 cSt, a base oil having a viscosity between 4-6 cSt and a base oil having a viscosity between 7-10 cSt product simultaneously from a single waxy raffinate product (viscosities as kinematic viscosity at 100 °C). By straightforward optimising the product slate and minimising the amount of non-base oil intermediate fractions it has been found possible to prepare base oils in a sufficiently high yield having a good Noack volatility properties. For example, base oils having a kinematic viscosity at 100 °C of between 3.5 and 6 cSt have been obtained which have a Noack volatility of between 6 and 14 wto.
It has been found that a lubricating base oil can be prepared starting from this waxy raffinate product which base oil comprises preferably at least 98 wt% saturates, more preferably at least 99.5 wto saturates and most preferably at least 99.9 wto. This saturates fraction in the base oil comprises between 10 and 40 wto of cyclo-paraffins. Preferably the content of cyclo-paraffins is less than 30 wto and more preferably less than 20 wto.
Preferably the content of cyclo-paraffins is at least 12 wto. The unique and novel base oils are~further characterized in that the weight ratio of 1-ring cyclo-paraffins relative to cyclo-paraffins having two or more rings is greater than 3 preferably greater than 5. It was found that this ratio is suitably smaller than 15.
The cyclo-paraffin content as described above is measured by the following method. Any other method resulting in the same results may also be used. The base oil sample is first separated into a polar (aromatic) phase and a non-polar (saturates) phase by making use of a high performance liquid chromatography (HPZC) method IP368/01, wherein as mobile phase pentane is used instead of hexane as the method states. The saturates and aromatic fractions are then analyzed using a Finnigan MAT90 mass spectrometer equipped with a Field desorption/Field Ionisation (FD/FI) interface, wherein FI
(a "soft" ionisation technique) is used for the semi-quantitative determination of hydrocarbon types in terms of carbon number and hydrogen deficiency. The type classification of compounds in mass spectrometry is determined by the characteristic ions formed and is normally classified by "z number". This is given by the general formula for all hydrocarbon species: CnH2n+z-Because the saturates phase is analysed separately from the aromatic phase it is possible to determine the content of the different (cyclo)-paraffins having the same stoichiometry. The results of the mass spectrometer are processed using commercial software (poly 32;
available from Sierra Analytics ZLC, 3453 Dragoo Park Drive, Modesto, California GA95350 USA) to determine the relative proportions of each hydrocarbon type and the average molecular weight and polydispersity of the saturates and aromatics fractions.
The base oil composition preferably has a content of aromatic hydrocarbon compounds of less than 1 wto, more preferably less than 0.5 wto and most preferably less than 0.1 wto, a sulphur content of less than 20 ppm and a nitrogen content of less than 20 ppm. The pour point of the base oil is preferably less than -30 °C and more preferably lower than -40 °C. The viscosity index is higher than 120. It has been found that the novel base oils typically have a viscosity index of below 140.
The base oils itself may find application as part of for example an Automatic Transmission Fluids (ATF), automotive (gasoline or diesel) engine oils, turbine oils, hydraulic oils, electrical oils or transformer oils and refrigerator oils.
The invention will be illustrated with the following non-limiting examples.
Example 1 A waxy raffinate product was obtained by feeding continuously a C5-C750 °C+ fraction of the Fischer-Tropsch product, as obtained in Example VII using the catalyst of Example III of WO-A-9934917 to a hydrocracking step (step (a)). The feed contained about 60 wto C30+ product. The ratio C60+/C30+ was about 0.55.
In the hydrocracking step the fraction was contacted with a hydrocracking catalyst. of Example 1 of EP-A-532118.
The effluent of step (a) was continuously distilled to give lights, fuels and a residue "R" boiling from 370 °C and above. The yield of gas oil fraction on fresh feed to hydrocracking step was 43 wto. The main part of the residue "R°' was recycled to step (a) and a remaining part was separated by means of a vacuum distillation into a waxy raffinate product having the properties as in Table 1 and a fraction boiling above 510 °C.
The conditions in the hydrocracking step (a) were: a fresh feed Weight Hourly Space Velocity (WHSV) of 0.8 kg/l.h, recycle feed WHSV of 0.2 kg/l.h, hydrogen gas rate = 1000 N1/kg, total pressure = 40 bar, and a reactor temperature of 335 °C.
Table 1 Density at 70C (kglm3) 779.2 vK@100 (cSt) 3.818 pour point (C) +18 Boiling point data as 5o 355 C
temperature at which a 100 370 C
wto is recovered.
Example 2 The waxy raffinate product of Example 1 was dewaxed to prepare a base oil by contacting the product with a dealuminated silica bound ZSM-5 catalyst comprising 0.70 by weight Pt and 30 wt% ZSM-5 as described in Example 9 of WO-A-0029511. The dewaxing conditions were 40 bar hydrogen, WHSV = 1 kg/l.h and a temperature of 340 °C.
The dewaxed oil was distilled into three base oil fractions: boiling between 378 and 424 °C (yield based on feed to dewaxing step was 14.2 wto), between 418-455 °C
(yield based on feed to dewaxing step was 16.3 wto) and a fraction boiling above 455 °C (yield based on feed to dewaxing step was 21.6 wto). See Table 2 for more details.
Table 2 Light Medium Heavy Grade Grade Gxade density at 20 C 805.8 814.6 822.4 pour point (C) < -63 < -51 - 45 kinematic viscosity at 19.06 35.0 40 C (cSt) kinematic viscosity at 100 C (cSt) 3.16 4.144 6.347 VI n.a. 121 134 Noack volatility (wto) n.a. 10.8 2.24 sulphur content (ppm) < 1 ppm < 1 ppm < 5 ppm saturates (ow) n.a. 99'.9 n.a.
Content of cyclo- n.a. 18.5 n.a.
paraffins (wt o ) ( *
) Dynamic viscosity as n.a. 3900 cP n.a.
measured by CCS at (*) as determined by means of a Finnigan MAT90 mass spectrometer equipped with a Field desorption/field ionisation interface on the saturates fraction of said base oil.
n.a.: not applicable n.d.: not determined Example 3 Example 2 was repeated except that the dewaxed oil was distilled into the different three base oil products of which the properties are presented in Table 3.
Table 3 Zight Medium Heavy Grade Grade Grade density at 20 C 809.1 817.2 825.1 pour point (C) < -63 < -51 - 39 kinematic viscosity at 23.32 43.01 40 C (cSt) kinematic viscosity at 100 C (cSt) 3.181 4.778 7.349 VI n.a. 128 135 Noack volatility (wto) n.a. 7.7 n.a.
sulphur content (ppm) < 5 ppm < 5 ppm < 5 ppm saturates (ow) 99.0 Dynamic viscosity as 5500 cP
measured by CCS at -40 C
Yield based on feed to 15.3 27.4 8.9 cat dewaxing step (wt%) Example 4 Example 2 was repeated except that the that the dewaxed oil was distilled into the different three base oil products and one intermediate raffinate (I.R.) of which the properties are presented in Table 4.
Table 4 Light I.R. Medium Heavy Grade Grade Grade density at 20 C 806 811.3 817.5 824.5 pour point (C) < -63 -57 < -51 - 39 Kinematic viscosity at 10.4 23.51 42.23 40 C (cSt) Kinematic viscosity at 100 C (cSt) 2.746 3.501 4.79 7.24 Noack volatility n.a. 6.8 1.14 sulphur content (ppm) < 5 ppm < 5 ppm < 5 ppm Saturates (ow) n.d. 99.5 Dynamic viscosity as 5500 cP
measured by CCS at Yield based on CDW feed 22.6 8.9 22.6 11.1 n.a.: not applicable n.d.: not determined Examples 2-4 illustrate that from the waxy raffinate product as obtained by the process of the present invention base oils are prepared in a high yield and wherein the base oils have excellent viscometric properties.
Claims (10)
1. Process to prepare a waxy raffinate product by (a) hydrocracking/hydroisomerisating a Fischer-Tropsch derived feed, wherein weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms in the Fischer-Tropsch product is at least 0.4 and wherein at least 30 wt% of compounds in the Fischer-Tropsch derived feed have at least 30 carbon atoms, (b) isolating from the product of step (a) a waxy raffinate product having a T10 wt% boiling point of between 200 and 450 °C and a T90 wt% boiling point of between 400 and 650 %C.
2. Process according to claim 1, wherein at least 50 wt%
of compounds in the Fischer-Tropsch derived feed have at least 30 carbon atoms.
of compounds in the Fischer-Tropsch derived feed have at least 30 carbon atoms.
3. Process according to any one of claims 1-2, wherein the Fischer-Tropsch derived feed is derived from a Fischer-Tropsch product comprising a C20+ fraction having an ASF-alpha value (Anderson-Schulz-Flory chain growth factor) of at least 0.925.
4. Process according to any one of claims 1-3, wherein the conversion in step (a) is between 25 and 70 wt%.
5. Process according to any one of claims 1-4, wherein the T90wt% boiling point of the waxy raffinate product is below 550 °C.
6. Process according to any one of claims 1-5, wherein the waxy raffinate product has a kinematic viscosity at 100 °C of between 3 and 10 cSt.
7. Use of the waxy raffinate product as obtained in a process according to any one of claims 1-6 to prepare a lubricating base oil.
8. Use according to claim 7 wherein the base oil is prepared by catalytically dewaxing the waxy raff mate product.
9. Use according to claim 8, wherein the cyclo-paraffin content in the saturates fraction of the lubricating base oil is between 12 and 20 wt%.
10. Use according to any one of claims 7-9, wherein the waxy raffinate product has a pour point of above 0 °C and has been transported to the location of base oil production in the solid state and under nitrogen blanketing.
Applications Claiming Priority (5)
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EP01400562 | 2001-03-05 | ||
EP01400562.3 | 2001-03-05 | ||
EP01402181.0 | 2001-08-16 | ||
EP01402181 | 2001-08-16 | ||
PCT/EP2002/002449 WO2002070630A1 (en) | 2001-03-05 | 2002-03-05 | Process to prepare a waxy raffinate |
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Families Citing this family (169)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MXPA03007088A (en) | 2001-02-13 | 2003-11-18 | Shell Int Research | Lubricant composition. |
AR032930A1 (en) | 2001-03-05 | 2003-12-03 | Shell Int Research | PROCEDURE TO PREPARE AN OIL BASED OIL AND GAS OIL |
AR032941A1 (en) | 2001-03-05 | 2003-12-03 | Shell Int Research | A PROCEDURE TO PREPARE A LUBRICATING BASE OIL AND BASE OIL OBTAINED, WITH ITS VARIOUS USES |
AR032932A1 (en) | 2001-03-05 | 2003-12-03 | Shell Int Research | PROCEDURE TO PREPARE A LUBRICANT BASED OIL AND OIL GAS |
US6699385B2 (en) | 2001-10-17 | 2004-03-02 | Chevron U.S.A. Inc. | Process for converting waxy feeds into low haze heavy base oil |
US6890423B2 (en) * | 2001-10-19 | 2005-05-10 | Chevron U.S.A. Inc. | Distillate fuel blends from Fischer Tropsch products with improved seal swell properties |
ATE325177T1 (en) | 2002-02-25 | 2006-06-15 | Shell Int Research | METHOD FOR PRODUCING A CATALYTICALLY DEPARAFFINED GAS OIL OR A CATALYTICALLY DEPARAFFINED GAS OIL MIXING COMPONENT |
JP4674342B2 (en) * | 2002-06-26 | 2011-04-20 | 昭和シェル石油株式会社 | Lubricating oil composition |
EP1534802B1 (en) | 2002-07-18 | 2005-11-16 | Shell Internationale Researchmaatschappij B.V. | Process to prepare a microcrystalline wax and a middle distillate fuel |
US6703353B1 (en) | 2002-09-04 | 2004-03-09 | Chevron U.S.A. Inc. | Blending of low viscosity Fischer-Tropsch base oils to produce high quality lubricating base oils |
US7132042B2 (en) * | 2002-10-08 | 2006-11-07 | Exxonmobil Research And Engineering Company | Production of fuels and lube oils from fischer-tropsch wax |
US20040129603A1 (en) * | 2002-10-08 | 2004-07-08 | Fyfe Kim Elizabeth | High viscosity-index base stocks, base oils and lubricant compositions and methods for their production and use |
US7144497B2 (en) * | 2002-11-20 | 2006-12-05 | Chevron U.S.A. Inc. | Blending of low viscosity Fischer-Tropsch base oils with conventional base oils to produce high quality lubricating base oils |
CN1723263A (en) | 2002-12-09 | 2006-01-18 | 国际壳牌研究有限公司 | Process for the preparation of a lubricant |
PT1576074E (en) * | 2002-12-09 | 2008-05-29 | Shell Int Research | Process to prepare a base oil having a viscosity index of between 80 and 140 |
US20080029431A1 (en) * | 2002-12-11 | 2008-02-07 | Alexander Albert G | Functional fluids having low brookfield viscosity using high viscosity-index base stocks, base oils and lubricant compositions, and methods for their production and use |
US20040154958A1 (en) * | 2002-12-11 | 2004-08-12 | Alexander Albert Gordon | Functional fluids having low brookfield viscosity using high viscosity-index base stocks, base oils and lubricant compositions, and methods for their production and use |
US20040154957A1 (en) * | 2002-12-11 | 2004-08-12 | Keeney Angela J. | High viscosity index wide-temperature functional fluid compositions and methods for their making and use |
US20040119046A1 (en) * | 2002-12-11 | 2004-06-24 | Carey James Thomas | Low-volatility functional fluid compositions useful under conditions of high thermal stress and methods for their production and use |
EP1464396A1 (en) * | 2003-03-10 | 2004-10-06 | Shell Internationale Researchmaatschappij B.V. | Process for preparing a lubricating base oil and a gas oil |
US6962651B2 (en) * | 2003-03-10 | 2005-11-08 | Chevron U.S.A. Inc. | Method for producing a plurality of lubricant base oils from paraffinic feedstock |
US7198710B2 (en) * | 2003-03-10 | 2007-04-03 | Chevron U.S.A. Inc. | Isomerization/dehazing process for base oils from Fischer-Tropsch wax |
CN1759167A (en) * | 2003-03-10 | 2006-04-12 | 国际壳牌研究有限公司 | Lubricant composition based on fischer-tropsch derived base oils |
US7141157B2 (en) * | 2003-03-11 | 2006-11-28 | Chevron U.S.A. Inc. | Blending of low viscosity Fischer-Tropsch base oils and Fischer-Tropsch derived bottoms or bright stock |
WO2004092061A1 (en) | 2003-04-15 | 2004-10-28 | Shell Internationale Research Maatschappij B.V. | Process for the preparation hydrogen and a mixture of hydrogen and carbon monoxide |
CN100587034C (en) * | 2003-05-27 | 2010-02-03 | 国际壳牌研究有限公司 | Process for preparing gasoline |
US20040256287A1 (en) * | 2003-06-19 | 2004-12-23 | Miller Stephen J. | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including fischer-tropsch wax, plus solvent dewaxing |
US20040256286A1 (en) * | 2003-06-19 | 2004-12-23 | Miller Stephen J. | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including Fischer-Tropsch wax |
ATE461264T1 (en) | 2003-06-23 | 2010-04-15 | Shell Int Research | METHOD FOR PRODUCING A LUBRICANT BASE OIL |
EP1641898B1 (en) * | 2003-07-04 | 2007-09-19 | Shell Internationale Researchmaatschappij B.V. | Process to prepare base oils from a fisher-tropsch synthesis product |
US7727378B2 (en) | 2003-07-04 | 2010-06-01 | Shell Oil Company | Process to prepare a Fischer-Tropsch product |
US20050077208A1 (en) * | 2003-10-14 | 2005-04-14 | Miller Stephen J. | Lubricant base oils with optimized branching |
JP2007509908A (en) * | 2003-10-29 | 2007-04-19 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for transporting methanol or hydrocarbon products |
US7053254B2 (en) * | 2003-11-07 | 2006-05-30 | Chevron U.S.A, Inc. | Process for improving the lubricating properties of base oils using a Fischer-Tropsch derived bottoms |
WO2005066319A1 (en) * | 2003-12-23 | 2005-07-21 | Chevron U.S.A. Inc. | Lubricating base oil with high monocycloparaffins and low multicycloparaffins |
US7195706B2 (en) * | 2003-12-23 | 2007-03-27 | Chevron U.S.A. Inc. | Finished lubricating comprising lubricating base oil with high monocycloparaffins and low multicycloparaffins |
EP1548088A1 (en) * | 2003-12-23 | 2005-06-29 | Shell Internationale Researchmaatschappij B.V. | Process to prepare a haze free base oil |
US7763161B2 (en) | 2003-12-23 | 2010-07-27 | Chevron U.S.A. Inc. | Process for making lubricating base oils with high ratio of monocycloparaffins to multicycloparaffins |
KR101303588B1 (en) | 2004-03-02 | 2013-09-11 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | Process to continuously prepare two or more base oil grades and middle distillates |
US8012342B2 (en) | 2004-03-23 | 2011-09-06 | Japan Energy Corporation | Lubricant base oil and method of producing the same |
US7045055B2 (en) * | 2004-04-29 | 2006-05-16 | Chevron U.S.A. Inc. | Method of operating a wormgear drive at high energy efficiency |
US7655132B2 (en) * | 2004-05-04 | 2010-02-02 | Chevron U.S.A. Inc. | Process for improving the lubricating properties of base oils using isomerized petroleum product |
GB2415435B (en) * | 2004-05-19 | 2007-09-05 | Chevron Usa Inc | Lubricant blends with low brookfield viscosities |
US7572361B2 (en) | 2004-05-19 | 2009-08-11 | Chevron U.S.A. Inc. | Lubricant blends with low brookfield viscosities |
US7473345B2 (en) | 2004-05-19 | 2009-01-06 | Chevron U.S.A. Inc. | Processes for making lubricant blends with low Brookfield viscosities |
US7384536B2 (en) | 2004-05-19 | 2008-06-10 | Chevron U.S.A. Inc. | Processes for making lubricant blends with low brookfield viscosities |
US7273834B2 (en) | 2004-05-19 | 2007-09-25 | Chevron U.S.A. Inc. | Lubricant blends with low brookfield viscosities |
US7465389B2 (en) * | 2004-07-09 | 2008-12-16 | Exxonmobil Research And Engineering Company | Production of extra-heavy lube oils from Fischer-Tropsch wax |
CN1981019B (en) * | 2004-07-09 | 2010-12-15 | 埃克森美孚研究工程公司 | Production of extra-heavy lube oils from fischer-tropsch wax |
CN1993451B (en) * | 2004-08-05 | 2011-09-28 | 切夫里昂美国公司 | Multigrade engine oil prepared from fischer-tropsch distillate base oil |
RU2007117151A (en) | 2004-10-08 | 2008-11-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) | METHOD FOR PRODUCING LOWER OLEFINS FROM CARBON-CONTAINING RAW MATERIALS |
US8202829B2 (en) * | 2004-11-04 | 2012-06-19 | Afton Chemical Corporation | Lubricating composition |
JP2008520786A (en) | 2004-11-18 | 2008-06-19 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Production method of base oil |
EP1812533B1 (en) | 2004-11-18 | 2011-02-16 | Shell Internationale Research Maatschappij B.V. | Process to prepare a gas oil |
JP4885442B2 (en) * | 2004-11-26 | 2012-02-29 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition and drive transmission device using the same |
US7252753B2 (en) | 2004-12-01 | 2007-08-07 | Chevron U.S.A. Inc. | Dielectric fluids and processes for making same |
US7510674B2 (en) | 2004-12-01 | 2009-03-31 | Chevron U.S.A. Inc. | Dielectric fluids and processes for making same |
US9012380B2 (en) | 2005-01-07 | 2015-04-21 | Nippon Oil Corporation | Lubricant base oil, lubricant composition for internal combustion engine and lubricant composition for driving force transmitting device |
JP5180437B2 (en) * | 2005-01-07 | 2013-04-10 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil |
JP6080489B2 (en) * | 2005-01-07 | 2017-02-15 | Jxエネルギー株式会社 | Lubricating base oil |
JP5114006B2 (en) * | 2005-02-02 | 2013-01-09 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
JP2012180532A (en) * | 2005-02-02 | 2012-09-20 | Jx Nippon Oil & Energy Corp | Lubricant composition for internal engine |
JP5087224B2 (en) * | 2005-02-10 | 2012-12-05 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for drive transmission device |
EP1851290A1 (en) * | 2005-02-24 | 2007-11-07 | Shell Internationale Research Maatschappij B.V. | Metal working fluid |
US7476645B2 (en) | 2005-03-03 | 2009-01-13 | Chevron U.S.A. Inc. | Polyalphaolefin and fischer-tropsch derived lubricant base oil lubricant blends |
US7655605B2 (en) | 2005-03-11 | 2010-02-02 | Chevron U.S.A. Inc. | Processes for producing extra light hydrocarbon liquids |
US20060219597A1 (en) * | 2005-04-05 | 2006-10-05 | Bishop Adeana R | Paraffinic hydroisomerate as a wax crystal modifier |
EP1869146B1 (en) | 2005-04-11 | 2011-03-02 | Shell Internationale Research Maatschappij B.V. | Process to blend a mineral and a fischer-tropsch derived product onboard a marine vessel |
US7851418B2 (en) | 2005-06-03 | 2010-12-14 | Exxonmobil Research And Engineering Company | Ashless detergents and formulated lubricating oil containing same |
TW200704770A (en) * | 2005-06-23 | 2007-02-01 | Shell Int Research | Oil composition |
JP5566025B2 (en) * | 2005-06-23 | 2014-08-06 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Insulating oil formulation |
US20070093398A1 (en) | 2005-10-21 | 2007-04-26 | Habeeb Jacob J | Two-stroke lubricating oils |
US8921287B2 (en) | 2005-11-02 | 2014-12-30 | Nippon Oil Corporation | Lubricating oil composition |
US20070151526A1 (en) * | 2005-12-02 | 2007-07-05 | David Colbourne | Diesel engine system |
US8053614B2 (en) * | 2005-12-12 | 2011-11-08 | Neste Oil Oyj | Base oil |
US7888542B2 (en) * | 2005-12-12 | 2011-02-15 | Neste Oil Oyj | Process for producing a saturated hydrocarbon component |
US7998339B2 (en) * | 2005-12-12 | 2011-08-16 | Neste Oil Oyj | Process for producing a hydrocarbon component |
KR101090930B1 (en) * | 2005-12-12 | 2011-12-08 | 네스테 오일 오와이제이 | Process for producing a hydrocarbon component |
US7850841B2 (en) * | 2005-12-12 | 2010-12-14 | Neste Oil Oyj | Process for producing a branched hydrocarbon base oil from a feedstock containing aldehyde and/or ketone |
JP5525120B2 (en) * | 2006-03-15 | 2014-06-18 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
JP5421514B2 (en) * | 2006-03-15 | 2014-02-19 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil |
EP2039745B1 (en) | 2006-03-15 | 2013-06-05 | Nippon Oil Corporation | Lube base oil, lubricating oil composition for internal combustion engine, and lubricating oil composition for drive transmission device |
JP5196726B2 (en) * | 2006-03-15 | 2013-05-15 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for drive transmission device |
BRPI0709604A2 (en) * | 2006-03-22 | 2011-07-19 | Shell Int Research | fluid composition, shock absorber, hydraulic system, vehicle, and use of a hydraulic fluid |
JP4945179B2 (en) * | 2006-07-06 | 2012-06-06 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
JP5137314B2 (en) | 2006-03-31 | 2013-02-06 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil |
JP2007270062A (en) * | 2006-03-31 | 2007-10-18 | Nippon Oil Corp | Lubricant base oil, lubricating oil composition and method for producing lubricant base oil |
JP4945178B2 (en) * | 2006-07-06 | 2012-06-06 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
JP4714066B2 (en) * | 2006-03-31 | 2011-06-29 | Jx日鉱日石エネルギー株式会社 | Method for hydrotreating wax |
JP5498644B2 (en) * | 2006-07-06 | 2014-05-21 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for drive transmission device |
JP4945180B2 (en) * | 2006-07-06 | 2012-06-06 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for wet clutch |
WO2007114132A1 (en) * | 2006-03-31 | 2007-10-11 | Nippon Oil Corporation | Lube base oil, process for production thereof, and lubricating oil composition |
US8299005B2 (en) | 2006-05-09 | 2012-10-30 | Exxonmobil Research And Engineering Company | Lubricating oil composition |
JP5207599B2 (en) * | 2006-06-08 | 2013-06-12 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition |
US7863229B2 (en) | 2006-06-23 | 2011-01-04 | Exxonmobil Research And Engineering Company | Lubricating compositions |
JP5633997B2 (en) * | 2006-07-06 | 2014-12-03 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil and lubricating oil composition |
EP2039746B1 (en) | 2006-07-06 | 2013-10-09 | Nippon Oil Corporation | Refrigerator oil composition |
JP2008013677A (en) * | 2006-07-06 | 2008-01-24 | Nippon Oil Corp | Refrigerating machine oil |
DE102007027344A1 (en) * | 2006-07-14 | 2008-01-17 | Afton Chemical Corp. | lubricant compositions |
US7879775B2 (en) * | 2006-07-14 | 2011-02-01 | Afton Chemical Corporation | Lubricant compositions |
US20080083657A1 (en) * | 2006-10-04 | 2008-04-10 | Zones Stacey I | Isomerization process using metal-modified small crystallite mtt molecular sieve |
US8026199B2 (en) | 2006-11-10 | 2011-09-27 | Nippon Oil Corporation | Lubricating oil composition |
EP1967571A1 (en) * | 2007-02-21 | 2008-09-10 | BP p.l.c. | Compositions and methods |
JP2008214369A (en) * | 2007-02-28 | 2008-09-18 | Showa Shell Sekiyu Kk | Fuel composition for diesel engine |
JP5518468B2 (en) | 2007-03-30 | 2014-06-11 | Jx日鉱日石エネルギー株式会社 | Hydraulic oil for shock absorber |
EP2135928B1 (en) * | 2007-03-30 | 2013-08-21 | Nippon Oil Corporation | Lubricant base oil, method for production thereof, and lubricant oil composition |
US20080260631A1 (en) | 2007-04-18 | 2008-10-23 | H2Gen Innovations, Inc. | Hydrogen production process |
RU2458969C2 (en) * | 2007-06-13 | 2012-08-20 | ЭкссонМобил Рисерч энд Энджиниринг Компани | Complex hydrotreatment with high-efficiency catalysts |
US20090001330A1 (en) * | 2007-06-28 | 2009-01-01 | Chevron U.S.A. Inc. | Electrical Insulating Oil Compositions and Preparation Thereof |
US20110047965A1 (en) * | 2007-08-31 | 2011-03-03 | Hayes Howard Richard | Use of a lubricant in an internal combustion engine |
WO2009034045A1 (en) | 2007-09-10 | 2009-03-19 | Shell Internationale Research Maatschappij B.V. | A process for hydrocracking and hydro-isomerisation of a paraffinic feedstock |
JP5342138B2 (en) * | 2007-12-28 | 2013-11-13 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition |
JP2009155639A (en) * | 2007-12-05 | 2009-07-16 | Nippon Oil Corp | Lubricant composition |
WO2009072524A1 (en) * | 2007-12-05 | 2009-06-11 | Nippon Oil Corporation | Lubricant oil composition |
WO2009071608A2 (en) * | 2007-12-07 | 2009-06-11 | Shell Internationale Research Maatschappij B.V. | Base oil formulations |
EP2072610A1 (en) | 2007-12-11 | 2009-06-24 | Shell Internationale Research Maatschappij B.V. | Carrier oil composition |
EP2075314A1 (en) | 2007-12-11 | 2009-07-01 | Shell Internationale Research Maatschappij B.V. | Grease formulations |
US8152869B2 (en) * | 2007-12-20 | 2012-04-10 | Shell Oil Company | Fuel compositions |
WO2009080679A1 (en) * | 2007-12-20 | 2009-07-02 | Shell Internationale Research Maatschappij B.V. | Process to prepare a gas oil and a base oil |
CN101998986B (en) * | 2007-12-20 | 2014-12-10 | 国际壳牌研究有限公司 | Fuel compositions |
EP2078743A1 (en) | 2008-01-10 | 2009-07-15 | Shell Internationale Researchmaatschappij B.V. | Fuel composition |
JP5483662B2 (en) * | 2008-01-15 | 2014-05-07 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition |
JP5806794B2 (en) * | 2008-03-25 | 2015-11-10 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for internal combustion engines |
JP5288861B2 (en) | 2008-04-07 | 2013-09-11 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition |
EP2100946A1 (en) * | 2008-09-08 | 2009-09-16 | Shell Internationale Researchmaatschappij B.V. | Oil formulations |
CN102227494A (en) * | 2008-10-01 | 2011-10-26 | 雪佛龙美国公司 | Process to make 110 neutral base oil with improved properties |
JP2010090252A (en) * | 2008-10-07 | 2010-04-22 | Nippon Oil Corp | Lubricant composition |
JP5806797B2 (en) * | 2008-10-07 | 2015-11-10 | Jx日鉱日石エネルギー株式会社 | Lubricating oil base oil and method for producing the same, lubricating oil composition |
JP5806795B2 (en) * | 2008-10-07 | 2015-11-10 | Jx日鉱日石エネルギー株式会社 | Lubricating oil base oil and method for producing the same, lubricating oil composition |
EP2341122B2 (en) | 2008-10-07 | 2019-04-03 | JX Nippon Oil & Energy Corporation | Lubricant base oil |
JP2010090251A (en) * | 2008-10-07 | 2010-04-22 | Nippon Oil Corp | Lubricant base oil, method for producing the same, and lubricating oil composition |
SG195528A1 (en) | 2008-10-07 | 2013-12-30 | Jx Nippon Oil & Energy Corp | Lubricant composition and method for producing same |
US8366908B2 (en) * | 2008-12-31 | 2013-02-05 | Exxonmobil Research And Engineering Company | Sour service hydroprocessing for lubricant base oil production |
EP2186871A1 (en) * | 2009-02-11 | 2010-05-19 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
JP5303339B2 (en) | 2009-03-31 | 2013-10-02 | Jx日鉱日石エネルギー株式会社 | Method for producing lubricating base oil |
US8999904B2 (en) | 2009-06-04 | 2015-04-07 | Jx Nippon Oil & Energy Corporation | Lubricant oil composition and method for making the same |
CN105695045A (en) | 2009-06-04 | 2016-06-22 | 吉坤日矿日石能源株式会社 | Lubricant oil composition |
JP5829374B2 (en) | 2009-06-04 | 2015-12-09 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition |
WO2010140446A1 (en) | 2009-06-04 | 2010-12-09 | 新日本石油株式会社 | Lubricant oil composition |
EP2446001B1 (en) * | 2009-06-24 | 2015-04-22 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
JP5689592B2 (en) | 2009-09-01 | 2015-03-25 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition |
WO2011055653A1 (en) * | 2009-11-09 | 2011-05-12 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Method of hydrocracking and process for producing hydrocarbon oil |
US20110189589A1 (en) * | 2010-01-29 | 2011-08-04 | The Johns Hopkins University | Composite porous catalysts |
EP2566940B1 (en) * | 2010-05-03 | 2019-01-09 | Shell International Research Maatschappij B.V. | Use of fischer-tropsch base oil for reducing the toxicity of used lubricating compositions |
BR112013027149A2 (en) | 2011-04-21 | 2017-01-10 | Shell Int Research | process for converting a solid biomass material |
BR112013027144A2 (en) | 2011-04-21 | 2017-01-10 | Shell Int Research | process for converting a solid biomass material |
AU2012245156A1 (en) | 2011-04-21 | 2013-10-31 | Shell Internationale Research Maatschappij B.V. | Process for converting a solid biomass material |
CA2833185A1 (en) | 2011-04-21 | 2012-10-26 | Shell Internationale Research Maatschappij B.V. | Liquid fuel composition |
JP5433662B2 (en) * | 2011-10-14 | 2014-03-05 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil |
JP5512642B2 (en) * | 2011-12-12 | 2014-06-04 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil |
US20130172432A1 (en) * | 2011-12-30 | 2013-07-04 | Shell Oil Company | Process for preparing a paraffin product |
JP5552139B2 (en) * | 2012-05-23 | 2014-07-16 | Jx日鉱日石エネルギー株式会社 | Lubricating base oil, lubricating oil composition, and method for producing lubricating base oil |
JP5746671B2 (en) * | 2012-09-24 | 2015-07-08 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition for drive transmission device |
EP2746367A1 (en) | 2012-12-18 | 2014-06-25 | Shell Internationale Research Maatschappij B.V. | Process to prepare base oil and gas oil |
US9988585B2 (en) | 2013-02-13 | 2018-06-05 | Jx Nippon Oil & Energy Corporation | Method for producing base oil for lubricant oils |
WO2015038693A1 (en) * | 2013-09-12 | 2015-03-19 | Chevron U.S.A. Inc. | A two-stage hydrocracking process for making heavy lubricating base oil from a heavy coker gas oil blended feedstock |
BR112016006757A2 (en) * | 2013-09-30 | 2017-08-01 | Shell Int Research | fischer-tropsch-derived diesel fractions and functional fluid formulation, and use of a fischer-tropsch-derived diesel fraction |
CN105593351A (en) * | 2013-09-30 | 2016-05-18 | 国际壳牌研究有限公司 | Fischer-Tropsch derived gas oil |
JP5847892B2 (en) * | 2014-06-25 | 2016-01-27 | Jx日鉱日石エネルギー株式会社 | Transmission oil composition for automobiles |
JP2014205858A (en) * | 2014-08-04 | 2014-10-30 | Jx日鉱日石エネルギー株式会社 | Lubricant composition |
JP2014205860A (en) * | 2014-08-04 | 2014-10-30 | Jx日鉱日石エネルギー株式会社 | Lubricant base oil and manufacturing method therefor, lubricant composition |
JP2014205859A (en) * | 2014-08-04 | 2014-10-30 | Jx日鉱日石エネルギー株式会社 | Lubricant base oil and manufacturing method therefor, lubricant composition |
WO2017218602A2 (en) * | 2016-06-13 | 2017-12-21 | Murray Extraction Technologies Llc | Improvement of properties of hydroprocessed base oils |
CN107663463B (en) * | 2016-07-29 | 2021-03-09 | 神华集团有限责任公司 | Method for producing low freezing point diesel oil by co-producing lubricating oil base oil |
WO2018077976A1 (en) | 2016-10-27 | 2018-05-03 | Shell Internationale Research Maatschappij B.V. | Process for preparing an automotive gasoil |
KR102026330B1 (en) | 2018-09-27 | 2019-09-27 | 에스케이이노베이션 주식회사 | Mineral based lubricant base oil with improved low temperature performance and method for preparing the same, and lubricant product containing the same |
CN110240938A (en) * | 2019-05-31 | 2019-09-17 | 国家能源投资集团有限责任公司 | For producing the system and method for lube base oil and high-melting-point Fischer-Tropsch wax |
EP4168513A1 (en) * | 2020-06-17 | 2023-04-26 | Shell Internationale Research Maatschappij B.V. | Process to prepare fischer-tropsch derived middle distillates and base oils |
US11873455B2 (en) * | 2020-12-30 | 2024-01-16 | Chevron U.S.A. Inc. | Process having improved base oil yield |
Family Cites Families (79)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2603589A (en) * | 1950-03-31 | 1952-07-15 | Shell Dev | Process for separating hydrocarbon waxes |
GB713910A (en) | 1951-08-14 | 1954-08-18 | Bataafsche Petroleum | Improvements in or relating to the isomerisation of paraffin wax |
US3965018A (en) | 1971-12-07 | 1976-06-22 | Gulf Research & Development Company | Process for preparing a concentrate of a polyalpha-olefin in a lubricating oil base stock |
US3876522A (en) | 1972-06-15 | 1975-04-08 | Ian D Campbell | Process for the preparation of lubricating oils |
JPS5624493A (en) | 1979-08-06 | 1981-03-09 | Nippon Oil Co Ltd | Central system fluid composition for automobile |
US4343692A (en) | 1981-03-27 | 1982-08-10 | Shell Oil Company | Catalytic dewaxing process |
GB2133035A (en) | 1982-12-31 | 1984-07-18 | Exxon Research Engineering Co | An oil composition |
JPS6044593A (en) | 1983-08-23 | 1985-03-09 | Idemitsu Kosan Co Ltd | General-purpose grease composition |
US4574043A (en) | 1984-11-19 | 1986-03-04 | Mobil Oil Corporation | Catalytic process for manufacture of low pour lubricating oils |
US4919788A (en) | 1984-12-21 | 1990-04-24 | Mobil Oil Corporation | Lubricant production process |
US4859311A (en) | 1985-06-28 | 1989-08-22 | Chevron Research Company | Catalytic dewaxing process using a silicoaluminophosphate molecular sieve |
CA1282363C (en) | 1985-12-24 | 1991-04-02 | Bruce H.C. Winquist | Process for catalytic dewaxing of more than one refinery-derived lubricating base oil precursor |
US5157191A (en) | 1986-01-03 | 1992-10-20 | Mobil Oil Corp. | Modified crystalline aluminosilicate zeolite catalyst and its use in the production of lubes of high viscosity index |
JPH0631174B2 (en) | 1987-11-19 | 1994-04-27 | 日本特殊陶業株式会社 | Method for producing reticulated silica whiskers-ceramics porous body composite |
EP0321307B1 (en) * | 1987-12-18 | 1993-04-21 | Exxon Research And Engineering Company | Method for isomerizing wax to lube base oils |
US5059299A (en) | 1987-12-18 | 1991-10-22 | Exxon Research And Engineering Company | Method for isomerizing wax to lube base oils |
US4943672A (en) | 1987-12-18 | 1990-07-24 | Exxon Research And Engineering Company | Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403) |
CA1310287C (en) | 1987-12-18 | 1992-11-17 | Exxon Research And Engineering Company | Process for the hydroisomerization of fischer-tropsch wax to produce lubricating oil |
US5252527A (en) | 1988-03-23 | 1993-10-12 | Chevron Research And Technology Company | Zeolite SSZ-32 |
US5053373A (en) | 1988-03-23 | 1991-10-01 | Chevron Research Company | Zeolite SSZ-32 |
ES2076360T3 (en) | 1989-02-17 | 1995-11-01 | Chevron Usa Inc | ISOMERIZATION OF LUBRICATING OILS, WAXES AND OIL WAXES USING A SILICOALUMINOPHOSPHATE MOLECULAR SCREEN CATALYST. |
US5456820A (en) * | 1989-06-01 | 1995-10-10 | Mobil Oil Corporation | Catalytic dewaxing process for producing lubricating oils |
US4983273A (en) | 1989-10-05 | 1991-01-08 | Mobil Oil Corporation | Hydrocracking process with partial liquid recycle |
IT218931Z2 (en) | 1989-10-31 | 1992-11-10 | Adler | FLOW CONCENTRATION LAMELLAR TYPE NON-RETURN VALVE |
EP0435670B1 (en) | 1989-12-26 | 1994-08-24 | Nippon Oil Co. Ltd. | Lubricating oils |
CA2047923C (en) | 1990-08-14 | 2002-11-19 | Heather A. Boucher | Hydrotreating heavy hydroisomerate fractionator bottoms to produce quality light oil upon subsequent refractionation |
US5053573A (en) * | 1990-09-14 | 1991-10-01 | Mobil Oil Corporation | Reduction of benzene content of reformate by reaction with cycle oils |
US5157151A (en) * | 1990-12-18 | 1992-10-20 | Isaac Angres | Salts of 1-adamantamine and formulations thereof |
GB9119504D0 (en) | 1991-09-12 | 1991-10-23 | Shell Int Research | Process for the preparation of naphtha |
RU2116332C1 (en) | 1992-10-28 | 1998-07-27 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Method and catalyst for preparing oil body |
US5362378A (en) | 1992-12-17 | 1994-11-08 | Mobil Oil Corporation | Conversion of Fischer-Tropsch heavy end products with platinum/boron-zeolite beta catalyst having a low alpha value |
US5370818A (en) | 1993-05-28 | 1994-12-06 | Potters Industries, Inc. | Free-flowing catalyst coated beads for curing polyester resin |
US5447621A (en) * | 1994-01-27 | 1995-09-05 | The M. W. Kellogg Company | Integrated process for upgrading middle distillate production |
EP0668342B1 (en) | 1994-02-08 | 1999-08-04 | Shell Internationale Researchmaatschappij B.V. | Lubricating base oil preparation process |
GB9404191D0 (en) | 1994-03-04 | 1994-04-20 | Imperial College | Preparations and uses of polyferric sulphate |
JPH07286190A (en) * | 1994-03-31 | 1995-10-31 | Tonen Corp | Lubricating oil composition |
CA2204278C (en) * | 1994-11-22 | 2003-12-23 | Exxon Research & Engineering Company | A method for upgrading waxy feeds using a catalyst comprising mixed powdered dewaxing catalyst and powdered isomerization catalyst formed into a discrete particle |
AR000314A1 (en) * | 1994-12-13 | 1997-06-18 | Shell Int Research | Hydrocarbon conversion procedures including catalytic hydrocracking |
MY125670A (en) | 1995-06-13 | 2006-08-30 | Shell Int Research | Catalytic dewaxing process and catalyst composition |
NO313086B1 (en) | 1995-08-04 | 2002-08-12 | Inst Francais Du Petrole | Process for preparing a catalyst, catalyst obtainable therewith, catalyst mixture obtained thereby, and process for the synthesis of hydrocarbons |
US5693598A (en) | 1995-09-19 | 1997-12-02 | The Lubrizol Corporation | Low-viscosity lubricating oil and functional fluid compositions |
AU715730B2 (en) | 1995-11-14 | 2000-02-10 | Mobil Oil Corporation | Integrated lubricant upgrading process |
DZ2129A1 (en) * | 1995-11-28 | 2002-07-23 | Shell Int Research | Process for producing base lubricating oils. |
EP0776959B1 (en) | 1995-11-28 | 2004-10-06 | Shell Internationale Researchmaatschappij B.V. | Process for producing lubricating base oils |
PT876446E (en) | 1995-12-08 | 2004-11-30 | Exxonmobil Res & Eng Co | HIGH PERFORMANCE HYDROCARBON OILS AND BIODEGRADABLE |
CA2259539A1 (en) | 1996-07-15 | 1998-01-22 | Chevron U.S.A. Inc. | Layered catalyst system for lube oil hydroconversion |
US5935417A (en) * | 1996-12-17 | 1999-08-10 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
GB9716283D0 (en) | 1997-08-01 | 1997-10-08 | Exxon Chemical Patents Inc | Lubricating oil compositions |
US7214648B2 (en) | 1997-08-27 | 2007-05-08 | Ashland Licensing And Intellectual Property, Llc | Lubricant and additive formulation |
US6090989A (en) | 1997-10-20 | 2000-07-18 | Mobil Oil Corporation | Isoparaffinic lube basestock compositions |
NZ504988A (en) | 1997-12-30 | 2001-08-31 | Shell Int Research | Cobalt and titania based fisher-tropsch catalyst |
US6059955A (en) * | 1998-02-13 | 2000-05-09 | Exxon Research And Engineering Co. | Low viscosity lube basestock |
JP2000080388A (en) * | 1998-09-03 | 2000-03-21 | Tonen Corp | Lubricant composition |
IT1301801B1 (en) * | 1998-06-25 | 2000-07-07 | Agip Petroli | PROCEDURE FOR THE PREPARATION OF HYDROCARBONS FROM SYNTHESIS GAS |
US6034040A (en) * | 1998-08-03 | 2000-03-07 | Ethyl Corporation | Lubricating oil formulations |
US6008164A (en) | 1998-08-04 | 1999-12-28 | Exxon Research And Engineering Company | Lubricant base oil having improved oxidative stability |
US6165949A (en) * | 1998-09-04 | 2000-12-26 | Exxon Research And Engineering Company | Premium wear resistant lubricant |
US6103099A (en) | 1998-09-04 | 2000-08-15 | Exxon Research And Engineering Company | Production of synthetic lubricant and lubricant base stock without dewaxing |
US6475960B1 (en) | 1998-09-04 | 2002-11-05 | Exxonmobil Research And Engineering Co. | Premium synthetic lubricants |
US6179994B1 (en) * | 1998-09-04 | 2001-01-30 | Exxon Research And Engineering Company | Isoparaffinic base stocks by dewaxing fischer-tropsch wax hydroisomerate over Pt/H-mordenite |
US6080301A (en) | 1998-09-04 | 2000-06-27 | Exxonmobil Research And Engineering Company | Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins |
US6332974B1 (en) * | 1998-09-11 | 2001-12-25 | Exxon Research And Engineering Co. | Wide-cut synthetic isoparaffinic lubricating oils |
US6110879A (en) * | 1998-10-15 | 2000-08-29 | Chevron U.S.A. Inc. | Automatic transmission fluid composition |
RU2235115C2 (en) | 1998-11-16 | 2004-08-27 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Catalytic dewaxing process and catalytic composition for carrying out this process |
ES2185445B1 (en) * | 1999-04-29 | 2004-08-16 | Institut Francais Du Petrole | FLEXIBLE PROCEDURE FOR PRODUCTION OF OIL BASES AND MEDIUM DISTILLATES WITH A CONVERSION-HYDROISOMERIZATION FOLLOWED BY A CATALYTIC DEPARAFINING. |
NL1015035C2 (en) * | 1999-04-29 | 2001-02-12 | Inst Francais Du Petrole | Flexible process for the production of base oils and distillation products by conversion hydroisomerization on a lightly dispersed catalyst, followed by catalytic dewaxing. |
US6872693B2 (en) * | 1999-05-24 | 2005-03-29 | The Lubrizol Corporation | Mineral gear oils and transmission fluids |
ITFO990015A1 (en) | 1999-07-23 | 2001-01-23 | Verdini Antonio | "POLYPEPTIDE DENDRIMERS AS UNIMOLECULAR CARRIERS OF DRUGS AND BIOLOGICALLY ACTIVE SUBSTANCES". |
JP4860861B2 (en) | 1999-07-26 | 2012-01-25 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for producing a lubricating base oil |
FR2798136B1 (en) | 1999-09-08 | 2001-11-16 | Total Raffinage Distribution | NEW HYDROCARBON BASE OIL FOR LUBRICANTS WITH VERY HIGH VISCOSITY INDEX |
US6642189B2 (en) | 1999-12-22 | 2003-11-04 | Nippon Mitsubishi Oil Corporation | Engine oil compositions |
US7067049B1 (en) | 2000-02-04 | 2006-06-27 | Exxonmobil Oil Corporation | Formulated lubricant oils containing high-performance base oils derived from highly paraffinic hydrocarbons |
US6255546B1 (en) * | 2000-02-08 | 2001-07-03 | Exxonmobile Research And Engineering Company | Functional fluid with low Brookfield Viscosity |
US6776898B1 (en) | 2000-04-04 | 2004-08-17 | Exxonmobil Research And Engineering Company | Process for softening fischer-tropsch wax with mild hydrotreating |
MXPA03007088A (en) | 2001-02-13 | 2003-11-18 | Shell Int Research | Lubricant composition. |
AR032930A1 (en) | 2001-03-05 | 2003-12-03 | Shell Int Research | PROCEDURE TO PREPARE AN OIL BASED OIL AND GAS OIL |
AR032932A1 (en) | 2001-03-05 | 2003-12-03 | Shell Int Research | PROCEDURE TO PREPARE A LUBRICANT BASED OIL AND OIL GAS |
DE10126516A1 (en) | 2001-05-30 | 2002-12-05 | Schuemann Sasol Gmbh | Process for the preparation of microcrystalline paraffins |
US6627779B2 (en) | 2001-10-19 | 2003-09-30 | Chevron U.S.A. Inc. | Lube base oils with improved yield |
-
2002
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- 2002-03-01 MY MYPI20020736A patent/MY139353A/en unknown
- 2002-03-04 BR BR0207891-0A patent/BR0207891A/en active Search and Examination
- 2002-03-04 EP EP02726138A patent/EP1366135B1/en not_active Expired - Lifetime
- 2002-03-04 WO PCT/EP2002/002366 patent/WO2002070629A1/en active IP Right Grant
- 2002-03-04 DE DE60238598T patent/DE60238598D1/en not_active Expired - Lifetime
- 2002-03-04 US US10/471,053 patent/US7285206B2/en not_active Expired - Lifetime
- 2002-03-04 EA EA200300973A patent/EA005089B1/en not_active IP Right Cessation
- 2002-03-04 AU AU2002256645A patent/AU2002256645B2/en not_active Ceased
- 2002-03-04 CN CNB028072669A patent/CN1249206C/en not_active Expired - Fee Related
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- 2002-03-04 JP JP2002570657A patent/JP2004528426A/en active Pending
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- 2002-03-05 JP JP2002570664A patent/JP2004522848A/en active Pending
- 2002-03-05 WO PCT/EP2002/002450 patent/WO2002070636A1/en active Application Filing
- 2002-03-05 AU AU2002256650A patent/AU2002256650B2/en not_active Ceased
- 2002-03-05 DE DE60201421T patent/DE60201421T2/en not_active Expired - Lifetime
- 2002-03-05 EP EP02702399A patent/EP1366138A1/en not_active Withdrawn
- 2002-03-05 US US10/469,952 patent/US7332072B2/en not_active Expired - Lifetime
- 2002-03-05 CN CNB028074203A patent/CN1245485C/en not_active Expired - Fee Related
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- 2002-03-05 NZ NZ527945A patent/NZ527945A/en unknown
- 2002-03-05 BR BRPI0207890-2A patent/BR0207890B1/en not_active IP Right Cessation
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- 2002-03-05 MX MXPA03007980A patent/MXPA03007980A/en active IP Right Grant
- 2002-03-05 CA CA002440071A patent/CA2440071A1/en not_active Abandoned
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- 2002-03-05 US US10/471,039 patent/US20040079675A1/en not_active Abandoned
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2003
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